DE1745784C3 - Fungicides and / or mite anicides - Google Patents

Description

O = C-N

R ₃

30th

35

The invention relates to fungicides and / or mite anicides for preventing or reducing the Damage to plants and inanimate organic matter by fungi and mites.

From U.S. Patent 2933 504 are fungicidal active 1 - (alkyloxycarbonyl) -benzimidazole-2-carbamic acid alkyl ester known. However, these are suitable bad as a fumigant, for example.

The invention relates to fungicides and / or mite anicides, which are characterized by a Content of a benzimidazole-2-carbamate of the general formula

H

60

in which R ₁ denotes an alkyl radical having 1 to 4 carbon atoms and R ₃ an alkyl radical having 1 to carbon atoms, a phenyl radical, a phenyl radical substituted by methyl, methoxy, nitro, cyano or halogen, a benzyl radical, a methyl, nitro, methoxy or Benzyl radical substituted with chlorine, a (cyclohexyl) methyl radical, a cyclohexyl radical, a methyl substituted cyclohexyl radical, an alkenyl radical with 3 to 10 carbon atoms or an {alkoxycarbonylf-alkyl radical with 3 to 6 carbon atoms, and on conventional carriers.

When used correctly, the agents according to the invention can penetrate the plants and become in move the plants. As a result, it is possible to protect an entire plant against mites and fungi to protect that only part of the plant is treated with the product in question; d. i.e., the included Compounds are system agents. When the funds are applied after the plant has already been attacked by a pathogenic fungus, they can enter the tissue and eliminate the infection, d. that is, the linkers also have healing properties.

Because of their excellent effects as fungicides and mite acides, the following compounds are used preferred in the agents according to the invention:

! (Methylcarbamoyl) -2-benzimidazole carbamine-

acid methyl ester, m.p.> 280 ° C, l- (ethylcarbamoyl) -2-benzimidazole carbamine-

acid methyl ester, F. 295 to 320 ⁰ C, HPropylcarbamoyO-S-benzimidazoIcarbamin-

acid methyl ester, mp 293 to 295 ° C (decomp.), 1- (butylcarbamoyl) -2-benzimidazole carbamic acid methyl ester, mp 312 ° C,
- (sec.Butylcarbamoyl) -2-benzimidazole carb-

amino acid methyl ester, m.p. 302 to 309 ⁰ C, l- (hexylcarbamoyl) -2-benzimidazoIcarbamine-

acid methyl ester, m.p. 306 to 316 ° C. l- (Isopropylcarbamoyl) -2-benzimidazole c2irb-

amic acid methyl ester, m.p. 293 to 319 ° C, l-ilsobutylcarbamoyl ^ -benzimidazolcarb-

amic acid methyl ester, m.p. 300 ° C, l- (Octylcarbamoyl) -2-beiizimidazolcarbamine-

acid methyl ester, F. 295 to 300 ⁰ C, HPhenylcarbamoyO-Z-bcnzimidazolcarbamin-

acid methyl ester, m.p. 215 ° C (decomp.), l - [(p-nitrophenyl) -ca; rbamoyl] -2-benzimidazole carbamic acid methyl ester,

F. 315 to 316 ° C (decomp.),
l - [(p-Tolyl) -carbamoyl] -2-benzimidazole-carbamate, m.p.> 300 ° C, - [(p-Methoxy phenyl) -carbamoyl] -2-benzimidazole-carbamate, m.p.> 320 ° C, - (hexylcarbamoyl) -2-benzimidazole carbamine-

isopropyl acid ester, m.p. 95 to 97 ° C,! - (EthoxycarbonylmethylcarbamoylJ-i-benzimidazole carbamic acid methyl ester,

F. 267 to 278 "C (dec.),
Isopropyl 1- (Allylcarbamoyl) -2-benzimidazolecarbamic acid, m.p.

Other connections that can be used are:

! - (MethylcarbamoylJ - ^ - benzimidazoliso-

butyl ester, m.p. 101 to 103 ° C, l- (hexylcarbamoyl) -2-benzimidazoliso-

butyl ester, ^{m.p. 101 to 103 0} C, 1- (ethoxycarbonylmethylcarbamoyl) -2-bi: nz-

imidazolisobutyl ester, mp 151 to 152 ° C (decomp.) 1- (ethoxycarbonylmethylcarbamoyl) -2-b: nzimidazole sec-butyl ester, M.p. 116 to 118 ° C.

C-NH-COOR ₁
H

(A)

= C-N

4th
\

R ₃

(B)

They can be made in different ways. For example, 1-carbamoyl-2-Benzimidazolcarbaminsäureester can he ^r are provided by 2-Benzimidazolcarbaminsäureester reacted with isocyanates according to the following equation:

(1)

30th

35

C-NH-C-OR ₁ + R ₃ NCO

40

45

C - NHC - OR ₁

In this equation, R ₁ and Rj have the meanings given above.

The reaction according to equation (1) can be carried out in various inert solvents, such as chloroform, Carbon tetrachloride, methylene chloride, benzene or cyclohexane can be carried out. Also mixed solvents can be used.

The reaction temperature is generally not particularly critical and can vary between The freezing point and the boiling point of the reaction mixture are, provided that only this boiling point is below is the temperature at which the reactants or products decompose. Room temperature is preferred.

The 1-carbamoyl-2-benzimidazole carbamic acid esters can also be prepared by first converting a 2-benzimidazole carbamic acid

55

60

65

Methyl 1- (butylcarbamoyl) -enzimidazole-2-carbamic acid is very particularly preferred.

The active ingredients contained according to the invention are named after structure (A); however, they can Also named after the tautomeric structure (B):

ester, phosgene and an acid-binding agent, the corresponding 1-chlorocarbonyl-2-benzimidazole carbamic acid ester and then converts it with ammonia or substituted amines according to the following reaction equations:

C - NH - C - OR ₁ + ClCCl

"5

20 base

C-NHCOR ₁ + 2HN

C-N

R ₃

O H

Il

C-NH-C-OR ₁ + NH HCl
NR ₃

In these equations, R ₁ and R _{3 have} the meanings mentioned above.

The reactions (2) and (3) can be carried out in solvents such as acetone, tetrahydrofuran, chloroform, Methylene chloride, benzene, cyclohexane or carbon tetrachloride. Mixtures too these solvents can be used.

Suitable bases are sodium hydroxide, sodium acetate, sodium carbonate, potassium carbonate, sodium bicarbonate, Trimethylamine, triethylamine, pyridine and many others. These bases can be as such or be applied in solution in a suitable solvent.

The reaction temperature is generally not decisive and can, as for the reaction (1) indicated, lie between the freezing point t and the boiling point of the reaction mixture, if only this boiling point is below the temperature at which the reactants and products decompose. It is preferable to work at room temperature.

1

. Among the many fungi against which the remedies are effective smd belong to Venturia inaequalis, the causative agent of Aplelschorf, Podosphaera leucotricha, the causative agent of powdery MeUau in apples, Uromyces phaseoii, the causative agent of bean rust, Cercospora apii, the "agent of dry spot disease in celery, Cercospora beticola, the causative agent of blue stain in sugar beet, Cercospora musae, the pathogen aer Sigotoka disease in bananas, Piricularia sp., the causative agent of Johnson's spot disease in bananas, Erysiphe cichoracearum, the causative agent of powdery Meltaus in sugar melons and other K-urbis plants, Penicillium digitatum, the causative agent of green mold in citrus fruits, Sphaerotneca humuli, the causative agent of powdery mildew in roses, Diplocarpon rosae, the causative agent of black spot disease in roses, Uncinula necator, the causative agent of powdery meltau in grapes. Coccomyces hiemalis, the causative agent of cherry leaf spot disease, Cladosporium carpophilum, the causative agent of scab in peaches, Erysiphe graminis hordei, the causative agent of Z'.verigem Meltau Barley, Monolinia (Sclerutinia) laxa ^ the causative agent of Brown rot in apricots, Monolinia (Sclerotinia) fructicola, the causative agent of brown rot in peaches, Piricularia oryzae, the causative agent of rice blight, Puccinia recondita, Puccinia coronata and Puccinia glumarum, the causative agent of leaf rust in wheat. Oats or grasses, Puccinia graminis tritici, the Stalk rust pathogen in wheat. Aspergillus niger, the causative agent of cottonseed boll rot and the putrefaction of many plant tissues after injury, Aspergillus terreus, a common one in the soil Fungus attacking vegetables, various species of Rhizoctonia, Fusarium and Verticillium. found in the soil and the roots and other underground parts of various plants attack various species of Penicillium that appear on fabrics, fibreboard, leather goods and paints flourish, species of Myrothecium, which include items such as shower curtains, carpets, and mats Attack items of clothing.

The milbenovicidal effect of the agents according to the invention enables them to be used for prevention the development of harmful mites or the gradual reduction of existing mite colonies. The movement of the mites is restricted. Hence, the enlargement of a colony of mites depends on it or the survival of a large colony of colony at a certain point largely from hatching the eggs laid by the mites at this point.

If these eggs are treated with an agent according to the invention or are placed on a surface containing such an agent, no living young will develop from the eggs. The eggs will also not hatch if they have been laid by a female mite that has been in contact with one of these agents or has ingested such an agent with her food. This disruption of the hatching of the eggs prevents the colony of mites from enlarging beyond the size existing at the time of treatment. Due to the high natural mortality rate of adult mites, the ovicidal effect also means that the mites can largely be removed from a site already infected by them within a short period of time. As long as the funds are on an upper ⁷⁸⁴ Y

there are mites on the surface or as long as the active substances are in the food of the New mite colonies cannot develop.

Many species of mites, the fruits, field crops, vegetables and ornamental plants under various conditions can be damaged by the inventive Combat means. This applies, for example, to the following types of mites: Panonychus ulmi (European red mite) and Tetranychus telarius (Two-spot mite), commonly referred to as "fruit mites"; these mites attack many deciduous tree fruits, such as apples, pears, cherries. Plums and peaches, on; Tetranychus atlanticus (Atlantic mite or strawberry mite), Tetranychus cinnabarinus (carmine-colored spider mite) and Tetranychus paeificus (Pacific mite); these mites attack cotton and numerous other crops on; Paratetranychus citri (red citrus mite) and others that attack citrus fruits, bryobia praetiosa (clover mite) that attacks clover, alfalfa and other crops, Aceria neoeynodomis, the grasses and attacks other plants, Tyrophagus lintneri, a dangerous pest for stored food and cultivated mushrooms, as well as Lepidoglyphus destiuctor, a mite that is in stock Kentucky blue grass seeds damage.

The active ingredients contained according to the invention enter the plants and move freely inside of the plants, d. H. they are system agents. Therefore, both fungi and mites can be found on plants fight in parts of plants that are far away from the treatment site. Considering this Activity, the funds can be applied to seeds. By treating cucumber seeds with a few Gram of one of these active ingredients per 50 kg of seeds can be powdered Meltau (Erysiphe cichoracearum) and control mites on the developing plants for periods in excess of 40 days. By applying the agent to the ground, you can prevent certain leaf diseases and mites in plants suppress that grow in the treated soil. By spraying or dusting leaves and plant stems or stems provide protection against fungi and mites for other parts of the plant, that have not been sprayed and for new foliage that will develop later.

For soil treatment, the active ingredients are used in quantities of 0.01 to 500 parts per million parts by weight of the soil. Preferred amounts for the treatment of seeds, tubers, bulbs or other parts of plants responsible for reproduction range from 0.03 to 6000 g of active ingredient per 50 kg of material to be treated. For the treatment of leaves, stems and fruits of living plants, the active ingredients are in amounts of 0.012 up to 60 kg of active ingredient applied per hectare. For immersion treatment of the roots of living plants the preferred amounts are in the range from 0.5 to 18,000 g of active ingredient per 380 liters of water or one other liquid carrier. For injection into the roots or trunks of living plants use amounts in the range of 0.01 to! 0 (XX) parts per million parts of water or other liquid Carrier preferred.

By treating with one of the agents according to the invention, parts of plants that become food or Harvested for fodder purposes, against rot

) other damage caused by fungi or mites is protected during processing, distribution and storage. If a liquid bath is used for this, it can contain the active ingredient in quantities in the range contain from 1 to 5000 parts per million parts by weight of 5 liquid. Dust and coating or Packing materials for this purpose contain 0.01 to

10% active ingredient.

Wood, leather, fabric, fiberboard, paper and other technical products of an organic nature ι ο can be coated or soaked with the agents according to the invention. The preferred amounts of active ingredient range from 0.025 to 95 percent by weight of the fabric to be protected. For the Soaking or storing the compounds are 15 amounts of active ingredient in the range from 0.001 to 30 percent by weight of the finished product preferred.

Also luggage, shoes, shower curtains, carpets, mats, clothes and other everyday items are against rot, fungus stains, mold and mite infestation through the Protected agents according to the invention. In this case, too, a surface treatment or a Deep treatment can be performed. Means for spraying, dipping or washing contain the 25 Active ingredient in quantities of 10 to 5000 parts per million. Liquids for aerosol treatment and Dusts contain the active ingredient in amounts of 0.1 to 20 percent by weight. Soaking solutions contain the Active ingredient in such concentrations that it can be used in amounts of 5 to 20,000 parts by weight per million Parts of the substance to be protected is deposited.

Painted surfaces can be protected against the formation of stains or mold by adding 5 to 20,000 parts per million of active ingredient to the paint before painting.

The damage to organic products in stock, such as grain. Seeds. Tubers. Onions. Meat or animal skin, mite, is minimized by treating the floors, walls and other parts of warehouses or buildings with one or more of the agents. The treatment is carried out by dusting. Spraying or spraying with aerosols, the preferred amounts being in the range from 0.05 to 1000 g of active ingredient per 93 m ^{2 of} the surface to be kept free from excessive mite infestation.

The healing of plant diseases with the means is strengthened if the treated plant so parts for one or more periods of 2 to 12 hours each after treatment with the active ingredient kept moist.

The activity of the active ingredients contained according to the invention can be increased by certain auxiliaries be that z. B. in the water in which the benzimidazole fungicides are dispersed. This Auxiliaries can be surfactants, oils. Wetting agents, enzymes, carbohydrates and organic

Be acids.

The preferred concentrations of surfactants in sprays are in the range of 10 to 10,000 parts per million parts of spray liquid. For dusts, the preferred amounts of surfactants are 1,000 to 300,000 parts per million parts of the agent to be applied.

The fungicides and milk novices of the invention contain one or more of the above Compounds mixed with a conventional carrier or conditioning agent. As an aid one generally uses inert solids, organic liquid solvents, organic ones liquid or aqueous diluents and surface active agents. Usually the Active ingredient content in the fungicides or mite ovids 1 to 95 percent by weight.

Compared to the 1-alkoxycarbonyl compounds U.S. Patent 2933504 have those of the invention Compounds contained inter alia the advantage that they can be used as fumigants for prevention fungal growth in moist harvested grains such as corn. So there is no direct contact of the fungicide with the grain to be protected to achieve the fungicides Effect required.

The following test results show the superiority of the Miuel according to the invention on fungicides known to be effective, namely N-trichloromethylthio-4-cyclohexene-1,2-dicarboximide. Dodecylguanidine acetate and sulfur.

Effect against apple scab

and

sSSS

WdCe “me, with a

vr.11 Antelscnon ivcmJna m ^ u «,, .., j, -...., ..-. the from Apiei: * - iR. “24 hours into one

SESSiTmiS and then kept in a greenhouse for 24 hours. "- Dk r ener small amount of surfactant and the test compound in concentrations of 80 1 and 3.2 sprayed ppm plants η turn for 24 hours in the humidity with a dispersion consisting of acetone..""Ammer given, it eight days later the plants were in the greenhouse After this period of time, the disease was determined.The results in the following table Sbcn the fungicidal effect (in percent) Ιϊ disappear with plants which have not been treated with an active ingredient.

Effect against real cucumber dew

In the preventive experiment, cucumbers were treated with a dispersion of acetone. Water, a small amount surface-active substance and the active ingredient m doses of 80, 16 and 3.2 ppm sprayed. One let dry the plants overnight in the greenhouse and then inoculate them by adding spores of the real cucumber meltau (Erysiphc cichoraccarum bcViuhtc the one from previously infected planters

409 636/181

had received. The plants were then left in the greenhouse for 8 days; this was followed by the fungicidal effect detected. The results in the table below indicate the effect (in percent) when compared of the treated plants with plants that had not been sprayed with an active ingredient.

To test the killing effect, cucumbers were inoculated by treating them with spores of pollinated with real cucumber meltau obtained from previously infected plants. 2 days later the plants were sprayed with a dispersion of acetone, water, a small amount of one surfactant and the active ingredient at a concentration of 80, 16 and 3.2 ppm. Man placed the plants in a greenhouse for 6 days and then assessed the intensity of the disease. the The results in the table below show the fungicidal effect (in percent) when the treated Plants compares with plants that have not been sprayed with an active ingredient.

Effect against mite eggs

Bean plants in the two-leaf stage were with

'adult mites of Tetranychus urticae

infected from 1pm to 4pm. The bean plants

were in a at 8 o'clock the next day

immersed weak tetraethyl pyrophosphate solution.

to kill the fully grown forms of the mite.

so that only the eggs remain. Against about

At 1 p.m. these plants were then sprayed until they ran off with the compound to be tested, which was present as a preparation in acetone-water together with a small amount of surface-active substance. After 5 days at 25 ± 0.56 ⁰ C, the leaves were examined under a magnifying glass to determine the percentage of eggs from which no mite was hatched. Under the test conditions, the untreated plants had about 5% eggs from which no mites had hatched.

connection

N-trichloromethylthio ^ -cyclohexene-l ^ -dicarboximid, 50% wettable powder (Römpp, Chemie-Lexikon, 5th edition [1962].

Col. 719)

Dodecylguanidine acetate, 70% wettable powder (Römpp, Chemie-Lexikon, 5th ed.

D 962], Col. 1025)

Wettable, very fine sulfur (W a 1 k e r, Diseases of vegetable crops, 1st Ed. [1952],

P. 199 to 201)

Methyl 1- (methylcarbamoyl) -2-benzimidazolecarbamic acid

L- (Ethylcarbamoyl) -2-benzimidazolecarbamic acid methyl ester

Methyl 1- (propylcarbamoyl) -2-benzimidazolecarbamic acid

HIsopropylcarbamoyl K ^ -benzimidazolecarbamic acid methyl ester

Methyl 1- (butylcarbamoyl) -2-benzimidazolecarbamic acid

! - (Isobutylcarbamoy'O ^ -benzimidazolecarbamic acid methyl ester

Methyl 1- (Sec-butylcarbamoyl) -2-benzimidazolecarbamic acid

Methyl 1- (hexylcarbamoyl) -2-benzimidazolecarbamic acid

1 - (Octylcarbamoyl ^ -benzimidazolecarbamic acid methyl ester

1- (Phenylcarbamoyl) -2-benzimidazolecarbamic acid mel hylcster

1- (p-Tolylcarbamoyl) -2-benzimidazo / ecarbamic acid c-methyl ester

L- (o-Tolylcarbamoyl) -2-benzimidazolecarbamic acid methyl ester

> 280
295-320
293-295 7crs
293-319
312
300

302-309
306-316
295-300

215dec.
> 300
~ 300zers.

Fungicidal effect (%) on foliage

Apple scab
(Vcnturia inaequalis)

P.
80 rävcnti
ppm
16 V
3.2 Ver
80 not
ppm
16 82 39 5 2 91 66 60 48 19th 100 87 100 33 100 95 78 99 86 100 99 92 100 92 99 98 78 94 98 99 99 79 99 86 100 100 69 100 99 100 95 37 100 55 99 99 36 98 98 100 97 19th 100 83 99 71 100 90 100 99 81 71 69 98 95 46 91 28

continuation

12th

connection

! - (m-Tolylcarbamoyl ^ -benziniidazolecarbamine-

acid methyl ester
l- (p-methoxyphenylcarbamoyl) -2-benzimidazole-

carbamic acid methyl ester

! - (o-NitrophenylcarbamoylVl-benzimidazole-

carbamic acid methyl ester

! - (m-NitrophenylcarbamoyO-I-benzimidazole-

carbamic acid methyl ester

Ho <: chlorophenylcarbamoyl) -2-benzimidazole-

carbamic acid methyl ester

1- (3,4-dichlorophenylcarbamoyl) -2-benzimidazoles

carbamic acid methyl ester

l- (3 <: chloro ^ -niethylphenylcarbamoyl) -2-benz-

imidazolecarbamic acid methyl ester

! - (p-Cyanphenylcarbamoyl ^ -benzimidazole-

carbamic acid methyl ester

1- (Benzylcarbamoyl l-2-benzimidazolecarbamine-

acid methyl ester
1- (4-Methoxybenzylcarbamoyl) -2-benzimidazole

carbamic acid methyl ester
l- (Cyclohexylcarbamoyl) -2-benzimidazolecarb-

amic acid methyl ester
! - (Cyclohexylmethylcarbamoyl ^ -bertzimidazole-

carbamic acid methyl ester
l- (2-Methylcyclohexylcarbamoyl) -2-benzimidazolecarbamic acid methyl ester l- (Isopropylcarbamoyl) -2-benzimidazole-

carbamate ethyl ester
1 ^ Hexylcarbarnoyl ^ -benzimidazoIecarbarnaläthylester
HMelhylcarbamoyU-I-benzimidazole carbamate isopropyl ester
1- (Butykarbamoyl) -2-benzimidazole carbamate isopropyl ester
! - (Hexylcarbamoyl ^ -benzimidazole carbamate isopropyl ester
l- (p-nitrophenylcarbamoyl) -2-benzimidazole-

carbamal isopropyl ester
1- (p-Methoxyphenylcarbamoyl) -2-benzimidazole

carbamate isopropyl ester
Mp-Cyanphenylcarbamoyiy ^ -benzimidazole-

carbamate isopropyl ester
HCyclohexylcarbamoyi ^ -benzimidazole-

carbamate isopropyl ester
1- (methylcarbamoyl) -2-benzimidazoleccarbamate bulyl ester

1 - (Hxylc ;;: bamoy1) -2-bcnzimidazolecarbarnate-butyl ester
MMethylcarbamoylj-I-benzimidazolecarbarnatsek-butylestcr
! - (Butylcarbamoyn ^ -bcnzimidazoiecarbamatsek.-butylcstcr

- 300 dec. > 32O 318-319

> 320 295-300

320 ~ 300 dec.

320

302-312 284-302 294-320 251-305 310-320 300 110

155-156 99-100 95-97 140-145 140-141

> 300 140-143

95-97

134-136

73-76

l-'ungidde effect (%) on foliage

Apple scab (Vcnturia inaeyualis)

Preventive ppm

80 16 97 91 100 .97

64 100 62 85

99 90 100 99 100 98 100 98 100 98 100 95

56 36 11 68 37 43 52 77 30 61 72 51

Destruction ppm

16 I.

80

91

71

99 77

78

78

92

85 86 95 68 100 80

96

97

99

83

92

99

100

99

98

71

65

78

97

90

74

87

68

47

27

49

73

82

65

36

36

61

71

33

11th

100 100

17th

18th

27

22nd

13th

25th

10

25th

12 11

22 7 6

22 7 0

96

55

89

97

72

94

71

98

47

10

20th

26th

18th

26th

11th

Continuation 14

connection

42
43
44
45
46
47
48
49
50
51

! - (Ethoxycarbonylmethylcarbamoyl ^ -benzimidazole carbamate methyl ester

! - (Ethoxycarbonylmethylcarbamoyl ^ -benzimidazole carbamate ethyl ester

! - (Ethoxycarbonylmethylcarbarnoyl ^ -benzimidazole carbamate isopropyl ester 1-iButoxycarbonylmethylcarbamoylJ ^ -benzimidazole carbamate isopropyl ester 1- (AUylcarbamoyl) -2-beiizimidazolecarbamate methyl ester

1- (Allylcarbamoyl) -2-benzimidazole carbamate ethyl ester

1- (Allylcarbamoyl) -2-benzimidazole carbamate isopropyl ester

! - (AllylcarbamoyO ^ -benzimidazole carbamate butyl ester

l - ^ - DecenylcarbamoylJ ^ -benzimidazole carbamate methyl ester

! - (DodecylcarbamoyO-Z -benzimidazolecarbamalmethylester

connection

N-trichloromethylthio ^ -cyclohexene-1,2-dicarboximide, 50% wettable powder (Römpp. Chemie-Lexikon, 5th edition [1962].

Col. 719)

Dodecylguanidine acetate 70% wettable powder (Römpp. Chemie-Lexikon. 5th ed.

[1962], col. 1025)

Wettable, very fine sulfur (Walker.

Diseases of vegetable crops, 1st Ed. [1952],

P. 199 to 201)

Methyl 1- (methylcarbamoyl) -2-ben7imidazolecarbamic acid

1- (Ethylcarbamoyl) -2-benzimidazolecarbamic acid methyl ester

Methyl 1- (propylcarbamoyl) -2-benzimidazolecarbamic acid

! - (Isopropylcarbamoyn ^ -bcnzimidazolecarbamic acid methyl ester

Methyl 1- (butylcarbamoyl) -2-benzimidazolecarbamic acid

! - (IsobutylcarbamoyD ^ -benzimidazolccarbamic acid methyl ester

F. (C)

267-278 dec.
275-276

89-91.5
103-105.5
293-297 dec.

Decomp.
134-136
Decomp.

72-80
195-215

Fungicidal effect (%) on foliage

Apple scab (Venturia inaequalis)

80

Preventive ppm

16

100

97

100

100

100

99

88

72

100

96

100

65

62

84

96

94

56

82

99

63

3.2

89

31

25th

17th

52

16

33

29

Destruction ppm

80

99

73

71

67

98

87

68

82

97

Fungicidal effect (%) on foliage

Hehler cucumber meltau
(Erysiphe cichoracearum)

Preventive
ppm

SO I 16 I 3 .:

Destruction ppm

80

100 97 99 80 99 82 99 62 100 90 99 87

40

15th

15th

15th

17th

97

100

100

99

99

100

100

39

99

97

85

93

99

98

96

63

27

83

30th

71

Milbcn-

ovicide

Effect,

Mortification

Tetra

nychus

urticac

ppm

2000

25 95

65 97

16

84

16

58

80

61

67

42

71

Toxicity.

approximate

deadly

Single dose:

(mg kg RaU

2 25 (

> 9 59I

4315

15th

continuation

! - (Sec-butylcarbamoylj ^ -benzimidazolecarbamic acid methyl ester H-hexylcarbamoyl ^ -benzimidazolecarbamic acid methyl ester Octylcarbamoyl ^ -benzimidazolecarbamic acid methyl ester ! - (PhenylcarbamoylK ^ -benzimidazolecarbamic acid methyl ester 1 - (p-TolylcarbamOj i) -2-benzimidazolecarbamic acid methyl ester ! - (o-TolylcarbamoylJ ^ -benzimidazoiecarbamic acid methyl ester Hm-TolylcarbarnoylJ ^ -benzimidazolecarbamic acid methyl ester Methyl l- (p-methoxyphenylcarbamoyl) -2-benzimidazolecarbamic acid ! - (o-NitrophenylcarbamoylK ^ -benzimidazolecarbamic acid methyl ester methyl l- (m-nitrophenylcarbamoyl) -2-benzimidazolecarbamic acid Ho-ChlGrphenylcarbamoylK ^ -benzirnidazolecarbamic acid methyl ester ! - (S ^ -DichlorophenylcarbamoylJ ^ -benzimidazoIecarbamic acid methyl ester Methyl 1- (3-chloro-4-methylphenylcarbamoyl) -2-benzimidazolecarbamic acid L- (p-Cyanophenylcarbamoyl) -2-benzimidazolecarbamic acid methyl ester 1- (Benzylcarbamoyl) -2-benzimidazolecarbamic acid methyl ester Methyl 1- (4-methoxybenzylcarbamoyl) -2-benzimidazolecarbamic acid methyl ester 1- (Cyclohexylcarbamoyl) -2-benzimidazolecarbamic acid I- (Cyclohexylmethylcarbamoyl) -2-benzimidazolecarbamic acid methyl ester 1- (2-Methylcyclohexylcarbamoyl) -2-benzimidazolecarbamic acid met hy lester 1- (isopropylcarbamoyl) -2-benzimidazole carbamate ethyl ester 1- (Hexylcarbamoyl) -2-benzimidazole carbamate ethyl ester 1- (Methylcarbamoyl) -2-benzimidazole carbamate isopropyl ester 1- (Butylcarbamoyl) -2-ben7.imidazolecarbamalisopropyl ester 1- (Hexylcarbamoyl) -2-benzimidazole carbamate isopropyl ester 1- (p-Nitrophenylcarbamoy!) -2-benzimidazole carbamate isopropyl ester 1- (p-Methoxyphenylcarbamoyl) -2-benzimidazole carbamate isopropyl ester

-ungic
P. ide we
hchic
Erysipl
preventive
ppm
16 kung
belt
e cich
3.2 %) on
cn melt
ordceai
Vern
80 Leaf\
ouch
around)
ichlui
ppm
16 sell
ig
3.2 Mite
ovicide
Effect.
Desoldering
(%)
Tetra
nychus
urticae
ppm
2000 Toxicity.
approximate
deadly
Single dose
rr.g kgRatiel 69 20th 2 91 56 25th 100 91 12th 100 93 20th 75 11000 95 72 25th 100 85 30th > 5,000 100 65 99 96 70 25th > 1000 99 83 0 75 67 22nd 15th > 11,000 30th 10 10 90 77 32 30th 7th 0 95 65 22nd 88 44 94 87 > 9 900 84 44 15th 97 72 10 99 92 37 52 37 7th 91 SO 60 60 30th 100 94 70 20th 77 67 7th 86 70 20th 91 32 5 98 85 42 85 22nd 98 85 > 11,000 90 27 02 50 0 100 94 70 70 > 7 5O0 99 55 100 84 92 72 12th 97 77 25th 90 25th 100 85 5 100 98 32 96 82 36 98 75 55 100 90 23 99 87 42 7 500 100 94 23 99 91 32 99 88 33 99 87 30th 88 62 99 82

409 636/186

36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51

Continued 18

Fungicidal effect (%) on foliage

Real cucumber meitau
(Erysiphe cichoracearuml

Hp -cyanophenylcarbamoyl ^ -benzimidazole carbamate isopropyl ester

1- (Cyclohexylcarbamoyl) -2-benzimidazole carbamate isopropyl ester

! - (MethylcarbamoyO-I-benzimidazole carbamate butyl ester

1- (Hexylcarbamoyl) -2benzimidazole carbamate butyl ester

HMethylcarbarnoyl VI-benzimidazole carbamate sec-butyl ester

! - (ButylcarbamoylJ ^ -benzimidazolecarbamalsek.-butylfcster

1- (Ethoxycarbonylmethylcarbamoyl) -2-benzimidazole carbamate methyl ester

HethoxycarbonylmethylcarbamoylKi-benzimidazole carbamate ethyl ester

1 - (Ethox ycarbonylmethylcarbamoy ^ -l-benzimidazole carbamate isopropyl ester HButoxycarbonylmethylcarbamoylJ ^ -benzimidazole carbamate-iso pro py tester HAllylcarbamoyl ^ -benzimidazole carbamate methyl ester

! - (Allylcarbamoyl ^ -benzimidazole carbamate ethyl ester

! - (Allylcarbamoyl K ^ -benzimidazole carbamate isopropyl ester

! - (Allylcarbamoyl ^ -benzimidazole carbamate butyl ester

l - ^ - Decenylcarbamoyl ^ -benzimidazole carbamate methyl ester

! - (Dodecylcarbamoyl I-I-benzimidazole carbamate methyl ester

P.
XO räventi
ppm
16 3.2 Ven
80 ichlur
ppm
16 98 87 32 94 13th 00 70 28 99 85 15th 3 0 10 3 0 95 28 5 99 65 76 i: 0 99 30th 0 99 99 -Ο 52 10 30th 8th 99 70 13th 98 90 97 34 18th 100 98 89 65 14th 99 85 99 86 45 99 18th 00 91 30th 100 72 45 0 0 93 65 5 99 28 98 80 12th 99 87

3.2

Mite aicids

Effect.

Mortification

Tetra

nychus

urticae

ppm

2000

30th

12th

77

67

38

42

45

Toxicity,

approximate

deadly

Single dose

(mg / kg rat)

7,500> 11,000

11000

> 11,000

> 11,000

Control of AspergilUis fiavus via the gas phase

Untreated corn kernels were moistened and inoculated in such a way that they could be kept in for 2 hours Immersed in water containing 3500 conidia of As]> ergillus fiavus per milliliter. After inoculation, the moisture content of the corn kernels was 20%. ss On the bottom of a 450 ml glass jar with a screw cap 900 mg of the dry compound to be tested were given. Next were rubber stoppers on the Arranged at the bottom of the glass vessel. Petri dishes (60 χ 15 mm), wel- (> o before the inoculated, moist corn kernels contained. The glass jars were then screwed on tightly closed. The glass vessels were kept at 25 ± 1 ° C. until untreated Control samples of corn kernels showed fungal colonies (> s.

The experiments were evaluated by determining the presence or absence of fungal growth on the corn kernels at 12.5x magnification. The results are reported as a percentage Control of Aspergillus fiavus growth.

(U.S. Patent 2,933,504)

ι /

C-NH-R ₃

= N-COCH ₃

N
H

(according to the invention)

Active ingredients
of the formula C:
Combat
by A. flavus R ₃ -CH ₃ Active ingredients
of formula B:
Combat
by A. flavus (%) ( ⁰ O) 0 - (CH ₂ J ₃ -CH ₃ 100 0 Cyclohexyl 100 0 -CH = CH-CH ₃ 100 0 Phenyl 100 0 100 0 100

With the active ingredients used according to the invention, therefore, 100% control is always achieved, with the corresponding 1-alkoxycarbonyl compounds (e) on the other hand, no control is achieved.

example 1

A wettable powder is made from the following ingredients:

Weight percent l-m-tolylcarbamoyl-2-benzimidazole

methyl carbamic acid 70.0

Diatomaceous earth 28.7

Sodium alkylarylsulfonates 1.0

Methyl cellulose 0.3

The above ingredients are mixed, crushed to grain sizes below 50μ and then again mixed.

The wettable powder obtained in this way becomes water in an amount corresponding to 454 g of active ingredient per each 378 liters of water were added. A modified phthalic acid-glycerol-alkyd resin is used for this mixture surfactant added at 400 parts per million. In an apple tree plantation every second tree is sprayed with this suspension until draining. The spraying takes place weekly once from April 25th to June 6th, the end of the growing season; from this point onwards the trees are sprayed at intervals of 2 weeks. The remaining trees in the plantation remain untreated.

At the beginning of September, all trees are carefully examined. The trees sprayed are healthy and free from mite and fungus infestation. Their fruits are faultless and of good size. The leaves of the unsprayed trees are heavily of apple scab (Venturia inaequalis) and powdery Meltau (Podosphaera leucotricha) infested. Also show the leaves of the unsprayed trees a strong infestation by the European red mite (Panonychus ulmi). The fruits on the unsprayed Trees have apple scabs and have remained small.

Example 2

The ingredients listed below are intimately mixed, in the air jet mill for particle (B) grind large sizes under 5 μ and then mix again :

Percent by weight of l-methylcarbamoyl-2-benzimidazole

methyl carbamic acid 50.0

Sodium dioctyl sulfosuccinate 1.0

Methyl cellulose of lower

Viscosity 0.3

Silica 48.7

Acid ginned cottonseed that already contains 85 g of tetramethylthiuram disulfide per 45.3 kg of seed is treated in a slurry treatment vessel with the above agent in an amount of 113g of active ingredient per 45.3 kg of seed treated. A similar approach of seeds is treated with tetramethykhiuram disulfide and only serves for comparison purposes. The two approaches are in alternating rows on the same field planted. The seeds treated only with tetramethylthiuram disulphide emerge in a good stand; however, many seedlings die after emergence. and the surviving plants show as a result Infestation by Rhizoctonia solani, poor growth. Most of the surviving seedlings show injuries from Rhizoctonia. The after-treated with the agent according to the invention After emergence, seeds show hardly any damage and grow quickly.

Example 3

A wettable powder is made from the following ingredients:

Weight percent

1 -Butylcarbamoyl-2-benzimidazole-

carbamic acid methyl ester 25

O- (methylcarbamoyl) -thiolaceto-

hydroxamic acid methyl ester 10

Oleic acid esters of sodium

isäthionat 2

Sodium Lauryl Sulphate 2

Diatomaceous Earth 61

The ingredients are processed into a uniform mixture by agitation in a mixer.

The mixture is then ground in the air jet mill to a particle size predominantly below 10 μ.

This wettable powder becomes water in soleher Amount added so that the mixture is 2.5 g of 0- (methylcarbamoyl) -thioacetohydroxamic acid methyl ester contains per liter of water. The suspension is applied once a week to one of two neighboring ones, with Fields planted with green beans in Florida in a spray density corresponding to 2 kg of 1-butylcarbamoyl - 2 - benzimidazole carbamic acid methyl ester sprayed per hectare. The test site is strong from the spotted mite Tetranychus bimaculatus and the Mexican bean beetle Epilachna varivestis infested. The field sprayed with the agent remains free from during the entire growth period the spotted mite and the Mexican bean beetle and makes a good harvest of green beans.

The unsprayed field is used by both pests attacked and so badly damaged that the harvest is significantly reduced. Similar fields that only with CH-methylcarbamoyl-hiolacetohydroxamic acid methyl ester are not injected by the Mexican bean beetle, but by attacked by the spotted mite.

Example 4

A dust concentrate is made from the following components:

Weight percent

1-PhenyIcarbamuyl-2-benzimidazole caibamic acid methyl ester 80

finely divided synthetic silica 20

The small parts are mixed, down to particle sizes Grind below 10 μ and mix again.

There are two experimental batches of a paint for houses produced in the same way with the Exception that - ^ ci the one approach together with the above agent in an amount corresponding to 0.5 percent by weight of the dry components of the paint Active ingredient, is ground, while the other approach does not contain a fungicide. With either of the two Approaches are painted on test boards. After a year of exposure to the weather in Florida, this shows Board that was painted with the non-fungicide-containing paint, strong fungus stains on the caused by Penicillium and other types of fungus. The one containing the agent according to the invention Painted board remains free of stains.

Example 5

An aqueous suspension concentrate is made from the following ingredients:

, _,, ..., percent by weight

l-butylcarbamoyl-2-benzimidazole

carbamic acid methyl ester 30.00

Sodium polyacrylate 0.35

Polyvinyl alcohol of lower

Viscosity 1.50

Water + (sodium hydroxide to pH 7.0, last

Component added) 68.15

The active ingredient is ground to a particle size below 0.6 mm and then with the other ingredients mixed, whereupon this mixture is crushed in the sand mill to grain sizes below 5 μ.

Fresh pine wood from the Sagemühle is made Immersed for 2 minutes in a bath containing the above suspension in a concentration corresponding to 400 parts Active ingredient per million parts by weight of the bath. Wood used for comparison will not immersed in the bath. All the wood is stacked together in a storage place and after 3 months examined. The wood treated with the agent is light and clean, while the untreated wood is heavily covered by green mold (Penicillium spp.).

Example 6

A granular agent is made from the following ingredients:

, -. , .. w · ι II- weight test / i

Grained Corn on the Cob '

(0.6 to 1.3 mm) 90

1 - Pentylcarbamoyl ^ -benzimidazolecarbamic acid ethyl ester K)

The active ingredient is dissolved in warm chloroform and the solution is sprayed onto the granular corn on the cob which is being circulated in a mixer. When evaporating of chloroform creates a granular substance that de Contains active ingredient absorbed.

A field in California is sown in the normal way with cotton, the according to the above Grains prepared according to the method are added to every other row of seeds. The grains are s.

upset that some are falling into the furrow some mix with the deck floor. The spreading density is 0.45 kg of active ingredient per 3600 m fur chen length. The other rows of plants remain untreated.

6 weeks after planting, there are many dci plants in the rows that have not received any treatment ten have died, and others show injuries caused by Rhizoctonia solani as well severe infestation by the Pacific mite (Tetranychus pacificus). In those treated with the agent Plant rows keep all plants healthy and free from mites. The effect on the mites is obvious a systemic effect.

B e i s ρ i e 1 7

An aerosol is made from the following components:

Weight percent 1 -isopropylcarbamoyl-2-benzimide-

ethyl azolecarbamate 3.0

Methylene chloride 22.0

Trichloromonofluoromethane 37.5

Dichlorodifluoromethane 37.5

The active ingredient is dissolved in the methylene chloride and the solution is poured into an aerosol container. The container is then charged with the chlorofluoromethane derivatives in the cold.

In a greenhouse, every other row of rose bushes is grown at intervals of sprayed lightly with the aerosol for a week. After 2 months of this treatment they are treated Plants healthy, have beautiful dark green leaves, and grow well. Show the untreated plants many discolored as a result of infection with Sphaerotheca humuli, the causative agent of powdery meltau in roses and curled leaves. Other leaves of the untreated plants are as a result of the attack

turned yellow by the Atlantic mite (Tetranychus atlanticus). As a result of the severe leaf damage the untreated plants grow much more slowly

Claims (2)

Patent claims: 1. Fungicid and / or mite elicid, characterized by a content of one Benzimidazole-2-carbamate of the general formula = N - COOR ₁ in which R ₁ denotes an alkyl group with 1 to 4 carbon atoms and R ₃ denotes an alkyl group with 1 to 12 carbon atoms, a phenyl group, a phenyl group substituted by methyl, methoxy, nitro, cyano or halogen, a benzyl group, a methyl group, nitro group, methoxy group or chlorine-substituted benzyl radical, a (cyclohexyl) methyl radical, a cyclohexyl radical, a cyclohexyl radical substituted by methyl, an alkenyl radical having 3 to 10 carbon atoms or an (alkoxycarbonyl) alkyl radical having 3 to 6 carbon atoms. 2. Fungicide and / or mite covid according to claim 1, characterized by a content of 1 - (Butylcarbamoyl) - benzimidazole - 2 - carbamic acid methyl ester.